Hydrochloric Acid → HCID 19090496, compound

HRID 1463665Notes

Reaction equation

HRID 1463665 reaction equation
[N:1]1[CH:6]=[CH:5][C:4]([CH2:7][C:8]([CH2:20][C:21]2[CH:26]=[CH:25][N:24]=[CH:23][CH:22]=2)([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=2[O:18][CH3:19])[C:9]([OH:11])=[O:10])=[CH:3][CH:2]=1.[B-](Br)(Br)(Br)[S+](C)C.Cl>ClC(Cl)C.O>[N:1]1[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[CH2:7][C:8]1([CH2:20][C:25]2[CH:26]=[CH:21][CH:22]=[CH:23][N:24]=2)[C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][C:17]=2[O:10][C:9]1=[O:11].[N:1]1[CH:6]=[CH:5][C:4]([CH2:7][C:8]([CH2:20][C:21]2[CH:22]=[CH:23][N:24]=[CH:25][CH:26]=2)([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=2[O:18][CH3:19])[C:9]([OH:11])=[O:10])=[CH:3][CH:2]=1

Participants

7

Reactant 3

HCID 313Hydrochloric AcidHCID 4181510Tribromoborane-methyl sulfideHCID 19922448HCID 19922448, compound

Product 2

HCID 19090496HCID 19090496, compoundYield 68%HCID 19922448HCID 19922448, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 63651,1-DichloroethaneSolvent

Procedure

To a suspension of α,α-bis(4-pyridinylmethyl)-2-methoxybenzene-acetic acid (7.7 g) in dichloroethane (150 ml) at 0° was added boron tribromide-methyl sulfide complex (1M in dichloromethane, 5 equivalents, 110 mmol, 110 ml). The mixture was warmed to room temperature, then heated at reflux for 20 h. After cooling to room temperature, 6N HCl (100 ml) was added, and the mixture was refluxed for 18 h. The mixture was cooled, diluted with water, and the layers were separated. The organic layer was extracted twice with 1N HCl (50 ml each). The combined aqueous layer was basified to pH 9 with concentrated ammonium hydroxide, and extracted with dichloromethane. The organic solution was dried over magnesium sulfate, filtered, and evaporated to give an oil. Purification by column chromatography (silica gel/3% methanol in dichloromethane) afforded 3,3-bis(pyridinylmethyl)-2(3H)benzofuranone [(4.7 g, 14.9 mmol, 68%) NMR (200 MHz, CDCl3) δ 3.31 (dd, 4H); 6.75 (m, 1H); 6.82 (dd, 4H); 7.14-7.30 (m, 3H); 8.35 (dd, 4H). Mass Calcd. for C20H16N2O2 : 316.1211. Found: 316.1202] and unreacted α,α-bis(4-pyridinylmethyl)-2-methoxybenzene-acetic acid (2.5 g, 7.2 mmol).

Workup

  1. temperatureheated
  2. temperatureat reflux for 20 h
  3. temperatureAfter cooling to room temperature
  4. temperaturethe mixture was refluxed for 18 h
  5. temperatureThe mixture was cooled
  6. customthe layers were separated
  7. extractionThe organic layer was extracted twice with 1N HCl (50 ml each)
  8. extractionextracted with dichloromethane
  9. dry with materialThe organic solution was dried over magnesium sulfate
  10. filtrationfiltered
  11. customevaporated
  12. customto give an oil
  13. customPurification by column chromatography (silica gel/3% methanol in dichloromethane)

Sources & evidence

ORD record
ord-b6c04c7cd53b4f7eaf56813722efe7ac
Source dataset
uspto-grants-1994_04
Patent number
US05300642

Reaction notes

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